Adhesion promoter

ABSTRACT

Compositions useful for improving the adhesion of coating compositions, such as dielectric film-forming compositions, include a hydrolyzed amino-alkoxysilane having a protected amino moiety. These compositions are useful in methods of improving the adhesion of coating compositions to a substrate, such as an electronic device substrate.

The present invention relates to the field of coating compositions, andmore particularly to improving the adhesion of certain coatingcompositions to a substrate.

Coating compositions are widely used in the electronics industry todeposit various organic-containing materials, such as polymericmaterials, on a variety of substrates. Often the substrates areinorganic or have inorganic areas on the surface to be coated. Forexample, coating compositions such as dielectric film-formingcompositions and bonding or adhesive compositions are often applied toglass, metal surfaces, and/or semiconductor surfaces such as silicon,gallium-arsenide, and silicon-germanium. Many organic materials do notadhere well to substrates having inorganic surfaces because they do notcontain groups that have an affinity for such surfaces. Accordingly, itis common practice to treat such substrate surfaces with an adhesionpromoter prior to disposing an organic-containing coating composition onit. Silanes are among the more common adhesion promoters usedindustrially.

Arylcyclobutene-based materials have been used in a wide variety ofapplications in the electronics industry due to their superiordielectric properties, excellent gap-fill and planarization properties,and low moisture adsorption. To use arylcyclobutene materials inapplications such as interlevel dielectrics and wafer bondingapplications, adequate adhesion of the arylcyclobutene material tovarious substrates (such as silicon, silicon nitride, gold, and copper)is required. Arylcyclobutene materials by themselves do not possesssufficient adhesion to these substrates, and therefore, an adhesionpromoter is usually applied to enhance adhesion prior to coating thearylcyclobutene material.

Various adhesion promoters are known for use with arylcyclobutenes. Forexample, U.S. Pat. No. 5,668,210 discloses certain alkoxysilanes asadhesion promoters for arylcyclobutenes. Only monosilanes are disclosedin this patent. These alkoxysilanes are hydrolyzed with 10 to 80% of thestoichiometric amount (that is mole %) of water. However, conventionaladhesion promoters are not able to meet the increasing requirements ofthe electronics industry for smaller feature sizes (<10 μm) and morecomplex chip designs, often resulting in delamination or other adhesivefailures. U.S. patent application Ser. No. 14/062,677 (Wang et al.)discloses certain poly(alkoxysilane) adhesion promoters containing asecondary amino group to improve the adhesion of dielectrics tosubstrates in applications having smaller feature sizes.

Newer dielectric materials are often base developable, meaning that theypossess base-reactive functionality, such as acid groups. Such acidgroup containing dielectric materials are incompatible with basicadhesion promoters, such as hydrolyzed amino group containingalkoxysilanes, in waste streams in various manufacturing processes. Forexample, when such acid group containing dielectric materials come intocontact with basic adhesion promoters, such as hydrolyzed amino groupcontaining alkoxysilanes, salts form which cause unwanted precipitationor clogging in drain lines, coating equipment, and the like. Thereremains a need for adhesion promoters suitable for use with dielectricmaterials having base-reactive functionality, and which are able to meetthe requirements of the electronics industry for <10 μm feature sizesand more complex chip designs, while being compatible with suchdielectric materials in waste streams. The present invention addressesone or more of these deficiencies.

The present invention provides a composition comprising: one or morehydrolyzed amino-alkoxysilanes having a protected amino moiety; water;and organic solvent. The present invention further provides acomposition comprising: one or more hydrolyzed amino-alkoxysilaneshaving a protected amino moiety; one or more oligomers chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof; water; andorganic solvent.

Also provided by the present invention is a process for manufacturing anelectronic device, comprising: providing an electronic device substratehaving a surface to be coated; treating the surface to be coated with acomposition comprising: one or more hydrolyzed amino-alkoxysilaneshaving a protected amino moiety; water; and organic solvent; disposing acoating composition comprising one or more oligomers chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof on the treatedsurface; and curing the coating composition.

Further, the present invention provides a process for manufacturing anelectronic device, comprising: providing an electronic device substratehaving a surface to be coated; treating the surface to be coated with acomposition comprising: one or more hydrolyzed amino-alkoxysilaneshaving a protected amino moiety; one or more oligomers chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof; water; andorganic solvent; and curing the oligomer.

As used throughout this specification, the following abbreviations shallhave the following meanings, unless the context clearly indicatesotherwise: ° C.=degree Celsius; g=gram; L=liter; mL=milliliter; ppm=partper million; mm=millimeter; μm=micron=micrometer; nm=nanometer; andÅ=angstrom. “Wt %” refers to percent by weight, based on the totalweight of a referenced composition, unless otherwise noted. All amountsare wt % and all ratios are molar ratios, unless otherwise noted. Allnumerical ranges are inclusive and combinable in any order, except whereit is clear that such numerical ranges are constrained to add up to100%. The articles “a”, “an” and “the” refer to the singular and theplural.

As used throughout the specification, “feature” refers to the geometrieson a substrate, and particularly on a semiconductor wafer. The term“alkyl” includes linear, branched and cyclic alkyl. Likewise, “alkenyl”refers to linear, branched and cyclic alkenyl. “Aryl” refers to aromaticcarbocycles and aromatic heterocycles. The term “oligomer” refers todimers, trimers, tetramers and other relatively low molecular weightmaterials that are capable of further curing. By the term “curing” ismeant any process, such as polymerization or condensation, thatincreases the molecular weight of a material or composition.

It has been surprisingly found that hydrolyzed amino-alkoxysilaneshaving a protected amine moiety (hydrolyzed amino-protectedalkoxysilanes) are particularly effective adhesion promoters for coatingoligomers chosen from polyarylene oligomers, poly(cyclic-olefin)oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, andmixtures thereof used in the manufacture of electronic devices. Suchcoating oligomers are useful in preparing dielectric coatings,photodefinable coatings, temporary bonding adhesives, and permanentbonding adhesives, among other applications.

A variety of hydrolyzed amino-alkoxysilanes are useful in the presentinvention. As used herein, the term “alkoxysilanes” includes“acyloxysilanes”. As used herein, the term “hydrolyzedamino-alkoxysilanes” refers to compounds having one or more primary orsecondary amino moieties, and one or more hydroxyl substituents directlyattached to one or more silicon atoms, and includes partially hydrolyzedand fully hydrolyzed amino-alkoxysilanes. Partially hydrolyzedamino-alkoxysilanes have at least one silicon atom in the moleculesubstituted with hydroxyl and at least one silicon atom in the moleculesubstituted with a hydrolyzable group such as (C₁-C₆)alkoxy or(C₁-C₆)acyloxy. Fully hydrolyzed amino-alkoxysilanes have silicon atomsin which all hydrolyzable substituents on the silicon atoms have beenreplaced with hydroxyls. In the present hydrolyzed amino-alkoxysilanes,the amino moiety is preferably separated from the silicon atom by one ormore non-nitrogen and non-silicon atoms, such as carbon.

The hydrolyzed amino-alkoxysilanes of the invention have a protectedamino moiety, that is, a primary or secondary amino moiety in thehydrolyzed amino-alkoxsilane has one of its hydrogens replaced with anamine protecting group moiety. Various amine protecting groups aresuitable for use in the present invention, provided such protectinggroups are removable (cleavable) by heat, acid, or a combinationthereof. Preferably, the amine protecting group is thermally cleavable,such as at a temperature of from 50 to 200° C., more preferably from 75to 200° C., even more preferably from 75 to 175° C., and yet morepreferably from 100 to 175° C. Suitable amine protecting groups usefulin the present invention include: carbamates such as 9-fluorenylmethylcarbamates, t-butyl carbamates, and benzyl carbamates; amides such asacetamides, trifluoroacetamides and p-toluenesulfonamides; benzylamines;triphenylmethylamines (tritylamines); and benzylideneamines. Carbamatesare the preferred amine protecting group, and t-butyl carbamates (t-BOC)are more preferred. Such amine protecting groups, their formation andtheir removal are well-known in the art. See, for example, T. W. Greenet al., Protective Groups in Organic Synthesis, Wiley-Interscience, NewYork, 1999.

Preferred hydrolyzed amino-alkoxysilanes are those of the formula (I):

wherein R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; R² is chosenfrom H, —R—SiZ₂(OR¹), (C₁-C₆)alkyl, (C₆-C₁₀)aryl and (C₇-C₁₅)alkaryl;each Z is independently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and—OR¹; and Y=an amine protecting group; wherein each R is optionallysubstituted with one or more of —(C₁-C₆)alkylidene-SiZ₂(OR¹) and—(C₁-C₆)alkylene-SiZ₂(OR¹), and wherein at least one R¹ is H. Each R ispreferably independently chosen from (C₁-C₆)alkylidene, (C₁-C₆)alkylene,and (C₂-C₆)alkenylene, each optionally substituted with one or more of(C₁-C₆)alkylidene-Si(Z)₂(OR¹) and (C₁-C₆)alkylene-Si(Z)₂(OR¹). Morepreferably, each R is independently chosen from (C₂-C₆)alkylidene,(C₂-C₆)alkylene, and (C₂-C₆)alkenylene. When an R group is substitutedwith (C₁-C₆)alkylidene-Si(Z)₂(OR¹) or (C₁-C₆)alkylene-Si(Z)₂(OR¹), it ispreferred that 1 to 2 of such groups are present. Each R¹ is preferablychosen from H, (C₁-C₄)alkyl and (C₂-C₆)acyl; more preferably from H,(C₁-C₃)alkyl and (C₂-C₄)acyl, and even more preferably each R¹═H. It ispreferred that each Z is chosen from (C₁-C₄)alkyl, (C₂-C₆)alkenyl and—OR¹; and more preferably each Z is —OR¹. Preferably, R² is chosen fromH, —R—SiZ₂(OR¹), (C₁-C₆)alkyl, and (C₇-C₁₅)alkaryl, and more preferablyH, —R—SiZ₂(OR¹), and (C₁-C₆)alkyl. It is preferred that Y is chosen from—C(O)—O—R³, —C(O)—R⁴, (C₇-C₂₀)alkaryl, ═CH—C₆H₅, and —SO₂—R⁵. R³ ismonovalent hydrocarbyl moiety having 1 to 20 carbons, preferably 2 to 18carbons, and more preferably 4 to 14 carbons. Preferred hydrocarbylmoieties for R³ are t-butyl, benzyl, and 9-fluorenylmethyl, and morepreferably t-butyl. R⁴ is a (C₁-C₆)alkyl, which may be substituted withone or more halogens. It is preferred that R⁴ is chosen from methyl andtrifluoromethyl. R⁵ is a monovalent hydrocarbyl moiety having 1 to 10carbons, and preferably 1 to 7 carbons. It is preferred that R⁵ istolyl. More preferably, Y is chosen from 9-fluorenylmethyloxy carbonyl,t-butoxy carbonyl, benzyloxy carbonyl, acetyl, trifluoroacetyl, benzyl,trityl, benzylidene, and tosyl.

Also preferred are hydrolyzed amino-poly(alkoxy)silanes of the formula(II):

wherein each R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; each R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; each Z isindependently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and —OR¹; andY=an amine protecting group; wherein each R is optionally substitutedwith one or more of —(C₁-C₆)alkylidene-SiZ₂(OR¹) and—(C₁-C₆)alkylene-SiZ₂(OR¹), and wherein at least one R¹ is H. Each R ispreferably independently chosen from (C₁-C₆)alkylidene, (C₁-C₆)alkylene,and (C₂-C₆)alkenylene, each optionally substituted with one or more of(C₁-C₆)alkylidene-Si(Z)₂(OR¹) and (C₁-C₆)alkylene-Si(Z)₂(OR¹). Morepreferably, each R is independently chosen from (C₂-C₆)alkylidene,(C₂-C₆)alkylene, and (C₂-C₆)alkenylene. When an R group is substitutedwith (C₁-C₆)alkylidene-Si(Z)₂(OR¹) or (C₁-C₆)alkylene-Si(Z)₂(OR¹), it ispreferred that 1 to 2 of such groups are present. Each R¹ is preferablychosen from H, (C₁-C₄)alkyl and (C₂-C₆)acyl; more preferably from H,(C₁-C₃)alkyl and (C₂-C₄)acyl, and even more preferably each R¹═H. It ispreferred that each Z is chosen from (C₁-C₄)alkyl, (C₂-C₆)alkenyl and—OR¹; and more preferably each Z is —OR¹. Preferably, R² is chosen fromH, —R—SiZ₂(OR¹), (C₁-C₆)alkyl, and (C₇-C₁₅)alkaryl, and more preferablyH, —R—SiZ₂(OR¹), and (C₁-C₆)alkyl. It is preferred that Y is chosen from—C(O)—O—R³, —C(O)—R⁴, (C₇-C₂₀)alkaryl, ═CH—C₆H₅, and —SO₂—R⁵. R³ is amonovalent hydrocarbyl moiety having 1 to 20 carbons, preferably 2 to 18carbons, and more preferably 4 to 14 carbons. Preferred hydrocarbylmoieties for R³ are t-butyl, benzyl, and 9-fluorenylmethyl, and morepreferably t-butyl. R⁴ is a (C₁-C₆)alkyl, which may be substituted withone or more halogens. It is preferred that R⁴ is chosen from methyl andtrifluoromethyl. R⁵ is a monovalent hydrocarbyl moiety having 1 to 10carbons, and preferably 1 to 7 carbons. It is preferred that R⁵ istolyl. More preferably, Y is chosen from 9-fluorenylmethyloxy carbonyl,t-butoxy carbonyl, benzyloxy carbonyl, acetyl, trifluoroacetyl, benzyl,trityl, benzylidene, and tosyl.

The present hydrolyzed amino-alkoxysilanes are preferably prepared byfirst protecting the amino moiety and then hydrolyzing one or more ofthe hydrolyzable groups on the silicon atom. In the alternative, thepresent hydrolyzed amino-alkoxysilanes are prepared by first hydrolyzingone or more of the hydrolyzable groups on the silicon atom and thenprotecting the amino moiety. Suitable amino-alkoxysilanes include, butare not limited to: 4-aminobutyl dimethyl methoxy silane;N-(2-aminoethyl)-3-aminopropyl dimethyl methoxy silane;N-(2-aminoethyl)-3-aminopropyl methyl dimethoxy silane;N-(2-aminoethyl)-3-aminopropyl trimethoxy silane; 3-aminopropyl methyldiethoxy silane; 3-aminopropyl triethoxy silane; 3-aminopropyltrimethoxy silane; bis[3-(trimethoxysilyl)propyl]amine;N¹,N¹-bis(3-(trimethoxysilyl)propyl)ethane-1,2-diamine;3-(trimethoxysilyl)-N-(2-(trimethoxysilyl)ethyl)-N-(3-trimethoxysilyl)propyl)propan-1-amine;and bis(3,3,9,9-tetramethoxy-2,10-dioxa-3,9-disilaundecan-6-yl)amine.Amino-alkoxysilanes are commercially available from a variety ofsources, such as Sigma-Aldrich (St. Louis, Mo.), or may be prepared byany suitable method known in the literature. The amino-alkoxysilanes maybe used without further purification, or may be purified using suitableprocedures known to those skilled in the art.

Various procedures for protecting amino moieties are known in the artand any of these procedures may be used to protect the amino moiety inthe present amino-alkoxysilanes. In general, an amine protecting groupprecursor compound is combined with the amino-alkoxysilane in a suitablesolvent, optionally in the presence of a catalyst, and allowed to reactfor a period of time at a suitable temperature. The selection of suchamine protecting group precursor compound, solvent, optional catalyst,time and temperature are well-known in the art. See, for example, T. W.Green et al., Protective Groups in Organic Synthesis,Wiley-Interscience, New York, 1999. For example, to form a t-butylcarbamate (or t-BOC) as the protected amino moiety, anamino-alkoxysilane is dissolved in an ether solvent and then combinedwith a desired amount of di-t-butyl dicarbonate and allowed to reactovernight at room temperature. In general, the molar ratio of amineprotecting group precursor compound to amino moiety is ≧0.8:1,preferably ≧0.9:1, yet more preferably ≧1:1, such as from 1:1 to 2:1,and even more preferably >1:1, such as from 1.05:1 to 1.5:1.

The amino-alkoxysilanes of the invention may be hydrolyzed according toprocedures known in the art, such as where the amino-alkoxysilane iscontacted with a desired amount of water, or by contacting theamino-alkoxysilane with water in the presence of a volatile solvent, orby simply combining the amino-alkoxysilane with a suitable solvent wherethe solvent has sufficient residual water content to effect the desiredlevel of hydrolysis. If a volatile solvent (or solvent mixture) is used,it is optionally removed prior to the hydrolyzed amino-alkoxysilanebeing incorporated into compositions comprising a coating oligomer.Alternatively, the hydrolysis is performed by combining theamino-alkoxysilane with a suitable organic solvent having sufficientresidual water to effect the desired level of hydrolysis. In anotheralternative, a desired amount of water is first combined with a desiredsolvent, and then this mixture is combined with the amino-alkoxysilane.The amount of water used is that amount sufficient to provide a desiredlevel of hydrolysis. Typically, the amount of water is from 0.01 to 3 wt% water, based on the total weight of the composition. Optionally, anacidic or basic catalyst may be employed in the hydrolysis reaction.When a separate catalyst is added, it is preferred that the catalyst isacidic.

The optional acidic or basic catalysts may be any acidic or basiccompound, or ion exchange resin or membrane, which will catalyze thehydrolysis of the amino-alkoxysilane. Examples of acidic catalystsinclude but are not limited to nitric acid, hydrochloric acid, sulfuricacid, trifluoroacetic acid, chloroacetic acid, methane sulfonic acid,and phosphoric acid. Examples of basic catalysts include but are notlimited to potassium hydroxide, sodium hydroxide, ammonium hydroxide,tetramethylammonium hydroxide, tetraethylammonium hydroxide, andtertiary amines. When present, the catalyst is used in amountssufficient to catalyze the hydrolysis reaction. The amount of catalystadvantageously employed will depend upon a number of factors includingthe desired rate of hydrolysis, the catalyst, the amino-alkoxysilaneused, and the degree of hydrolysis desired. Preferably, the catalyst ispresent in molar ratios of 0.1:1 to 3:1 catalyst to amino-alkoxysilane.More preferably, the catalyst is present in a molar ratio of 0.2:1 to1.5:1, and yet more preferably 0.25:1 to 1:1, catalyst toamino-alkoxysilane.

In the hydrolysis reaction, the present amino-alkoxysilane, water,solvent, and optional catalyst are mixed until the desired hydrolysis iscomplete. While the time to complete the hydrolysis will vary dependingon a number of factors, including the specific reactants employed andthe level of hydrolysis desired, in general, the hydrolysis is completein 1 minute to 48 hours, preferably from 1 minute to 24 hours, and morepreferably from 1 minute to 12 hours. In general, because of the lowlevels of water used, the amino-alkoxysilane, water, and solvent willform a single-phase mixture. Preferably, the organic solvent, or organicsolvent mixture, is selected such that the organic solvent is misciblewith water in all proportions. In general, the mixture is agitated for 1minute to 2 hours after a single phase is obtained to complete thehydrolysis reaction. The temperature at which hydrolysis is conducted ispreferably from about 15 to 100° C., more preferably from 20 to 50° C.,and most preferably from 20 to 25° C. Hydrolysis rates increase withincreasing temperatures. Preferably, the hydrolysis is conducted in theabsence of a catalyst. In such procedure, the desired amount of water ismixed with the desired solvent, then combined with theamino-alkoxysilane and stirred for a sufficient period of time for thedesired extent of hydrolysis to occur. Preferably, the solvent used isthe same solvent used to prepare the treating (adhesion promoter)composition. This method may take up to several days depending upon theparticular amino-alkoxysilane and the temperature at which hydrolysisoccurs. In some applications this method may be preferred when residualcatalyst levels have an adverse effect on subsequent use of thehydrolyzed amino-alkoxysilane.

While not wishing to be bound by theory, it is believed that hydrolysisof amino-alkoxysilanes produces a mixture of partially hydrolyzed andfully hydrolyzed amino-alkoxysilanes, and possibly oligomerizedamino-alkoxysilanes. The term “hydrolyzed amino-alkoxysilane”is meant toinclude partially hydrolyzed and fully hydrolyzed amino-alkoxysilanes,individually and in admixture, each optionally in the presence ofnonhydrolyzed amino-alkoxysilanes or oligomerized amino-alkoxysilanes.Oligomerization occurs when a hydrolyzed or partially hydrolyzedamino-alkoxysilane reacts with another amino-alkoxysilane to producewater and an Si—O—Si bond. As used herein, the term “hydrolyzedamino-alkoxysilane” encompasses all levels of hydrolysis of theamino-alkoxysilane, that is, partially hydrolyzed and fully hydrolyzed,as well as oligomerized amino-alkoxysilane.

Mixtures of hydrolyzed amino-protected alkoxysilanes may be used in thepresent invention, such as a mixture of two or moreamino-protected-alkoxysilanes of formula (I), or a mixture of two ormore amino-protected-alkoxysilanes of formula (II), or a mixture of twoor more amino-protected-alkoxysilanes of formula (I) and two or moreamino-protected-alkoxysilanes of formula (II). Alternatively, a mixtureof one or more hydrolyzed amino-protected-alkoxysilanes of the inventionwith one or more hydrolyzed amino-alkoxysilanes having unprotected aminomoieties may be used. When a mixture of protected and unprotectedamino-alkoxysilanes is used, it is preferred that the ratio of protectedto unprotected amino-alkoxysilanes is in the range of 80:20 to 99:1,preferably from 85:15 to 99:1, and more preferably from 90:10 to 99:1.Suitable unprotected amino-alkoxysilanes useful in such mixture arethose of formulae (I) and/or (II) where Y is H.

Adhesion promoter compositions of the invention comprise one or morehydrolyzed amino-protected-alkoxysilanes, water and one or more organicsolvents. Optionally, the present adhesion promoter compositions mayfurther comprise one or more hydrolyzed amino-alkoxysilanes having anunprotected amino moiety. Water may be added separately to thecomposition, or may be present with the hydrolyzedamino-protected-alkoxysilane, or may be present in the organic solventused. The solvent used in the present adhesion promoting compositionscan be any single organic solvent or mixture of two or more organicsolvents in which the hydrolyzed amino-alkoxysilane is soluble.Exemplary organic solvents include, without limitation: aromatichydrocarbons such as toluene, xylene, mesitylene and alkylnaphthalenes;alcohols such as 2-methyl-1-butanol, 3-methyl-1-butanol,4-methyl-2-pentanol, and methyl isobutyl carbinol; diols such as 1,2propane diol, 1,3 proapane diol, 1,2 butane diol, 1,4 butandiol, 1,2,hexane diol, 1,6 hexane diol, dipropylene glycol, tripropylene glycol;esters such as ethyl lactate, propylene glycol methyl ether acetate(PGMEA), 3-methoxy-1-butylacetate and methyl 2-hydroxyisobutyrate;lactones such as gamma-butyrolactone; lactams such asN-methylpyrrolidinone; ethers such as anisole, propylene glycol methylether (PGME), propylene glycol ethyl ether (PGEE), propylene glycolpropyl ether (PGPE), propylene glycol phenyl ether (PGPHE), dipropyleneglycol methyl ether (DPGME), tripropylene glycol monomethyl ether anddipropylene glycol dimethyl ether isomers (commercially available fromThe Dow Chemical Company as Proglyde™ DMM); ketones such ascyclohexanone and methylcyclohexanone; and mixtures thereof.

Optionally, the present adhesion promoter composition may comprise oneor more additives chosen from a metal passivation agent and a latentacid catalyst. Metal passivation agents may be useful to preventcorrosion of metal contained on the surface of the substrate to betreated. Such corrosion may result from residual acid catalyst used inthe hydrolysis of the present amino-alkoxysilanes. Various metalpassivation agents are known in the art, and any may be used in thepresent compositions. Suitable metal passivation agents include, withoutlimitation, triazole, substituted triazoles, benzotriazole, substitutedbenzotriazoles tetrazole, substituted tetrazoles, imidazole, substitutedimidazoles, benzimidazole, substituted benzimidazoles, and the like.Such metal passivation agents are typically used in an amount of from 0to 5000 ppm, preferably from 0 to 1000 ppm, and more preferably from 1to 1000 ppm. Latent acid catalysts may be added to the adhesion promotercompositions to help cleave the amine protecting group from thehydrolyzed amino-alkoxysilanes. Latent acid catalysts include thermalacid generators and photoacid generators. A variety of thermal acidgenerators and photoacid generators are known in the art, and any may beused in the present invention. Such latent acid catalysts are typicallypresent in the adhesion promoter compositions in molar ratios of 0.1:1to 3:1 latent catalyst to hydrolyzed amino-alkoxysilane. Morepreferably, the latent catalyst is present in a molar ratio of 0.2:1 to1.5:1, and yet more preferably 0.25:1 to 1:1, latent catalyst tohydrolyzed amino-alkoxysilane.

In general, the present adhesion promoter compositions comprise from0.01 to 10 wt % of amino-alkoxysilane and/or hydrolyzedamino-alkoxysilane, from 0.01 to 3 wt % water, and from 90 to 99.98 wt %of organic solvent. Preferably, the adhesion promoter compositionscomprise from 0.01 to 5 wt % of amino-alkoxysilane and/or hydrolyzedamino-alkoxysilane, more preferably from 0.01 to 3 wt %, and even morepreferably from 0.05 to 2 wt %. The amount of water is preferably from0.05 to 2 wt %, and more preferably from 0.1 to 2 wt %. Preferably, theadhesion promoter compositions comprise from 90 to 99.95 wt % of organicsolvent, more preferably from 95 to 99.95 wt %, and even more preferablyfrom 98 to 99.9 wt %. Particularly preferred compositions comprise from0.1 to 2 wt % of amino-alkoxysilane and/or hydrolyzedamino-alkoxysilane, from 0.05 to 1.5 wt % water, and from 97 to 99.95 wt% of organic solvent.

The present adhesion promoter compositions are typically applied to anelectronic device substrate to improve the adhesion of subsequentlyapplied coating compositions. The present process of manufacturing adevice, comprises: providing a device substrate having a surface to becoated; treating the surface to be coated with a composition comprisinga hydrolyzed amino-alkoxysilane having a protected amino moiety, water,and an organic solvent; and disposing a composition comprising anoligomer chosen from polyarylene oligomers, poly(cyclic-olefin)oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, andmixtures thereof on the treated surface.

The device may be any suitable substrate used in the manufacture ofelectronic devices, including, without limitation: packaging substratessuch as multichip modules; flat panel display substrates; integratedcircuit substrates, substrates for light emitting diodes (LEDs),semiconductor wafers, polycrystalline silicon substrates, and the like.Exemplary device substrates which can be coated with the coatingcomposition include metals such as aluminum, copper, gold, silver,titanium, tantalum, nickel, tin, tin-alloys, and the like; ceramics suchas alumina, silica, sapphire, MgO, BeO, including spinets, aluminumnitride, boron nitride, silicon nitride, silicon carbide, and galliumarsenide; glass such as fiber glass, lime glass, flint glass,borosilicate glass, Gorilla™ glass, Pyrex™ glass and Vycor™ glass; andsemiconductor wafers. A wide variety of semiconductor wafers may beemployed in the present invention. As used herein, the term“semiconductor wafer” is intended to encompass “an electronic devicesubstrate,” “a semiconductor substrate,” “a semiconductor device,” andvarious packages for various levels of interconnection, including asingle-chip wafer, multiple-chip wafer, packages for various levels, orother assemblies requiring solder connections. Particularly suitablesubstrates are patterned wafers, such as patterned silicon wafers andpatterned gallium-arsenide wafers. Such wafers may be any suitable size,such as 200 mm to 300 mm diameter, although wafers having smaller andlarger diameters may be used. The term “semiconductor substrate” isdefined to mean any construction comprising semiconductive material,including but not limited to bulk semiconductive material such as asemiconductive wafer, either alone or in assemblies comprising othermaterials thereon, and semiconductive material layers, either alone orin assemblies comprising other materials. A semiconductor device refersto a semiconductor substrate upon which at least one microelectronicdevice has been or is being fabricated. Optionally, the substrate may betreated by any suitable known process, such as acid etching, oxygenplasma etching or RCA cleaning, prior to the application of the coatingcomposition to control surface chemistry.

The device substrate surface is treated by contacting it with thepresent adhesion promoter composition using any suitable method.Exemplary methods well-known in the art include spin-coating, curtaincoating, spray coating, roller coating, dip coating, screen printing,and gas phase deposition, among other methods. In the semiconductormanufacturing industry, spin-coating is preferred to take advantage ofexisting equipment and processes. After being disposed on a substratesurface, the solvent is removed from adhesion promoter composition theprior to the next step, and the amino moiety in the hydrolyzedamino-alkoxysilane is deprotected, that is, the amine protecting groupis cleaved (removed). Solvent removal is typically achieved by heating(baking) the substrate for a period of time. Preferably, the treatedsurface is subjected to conditions that remove the solvent and cleavethe amine protecting group in a single step. For a thermally cleavableamine protecting group, such as t-butyl carbamate, the substrate issubjected to a temperature sufficient to cleave the amine protectinggroup. When a thermal acid generator is used as the latent acidcatalyst, the treated substrate is typically subjected to a temperaturesufficient to generate the acid catalyst. Suitable temperatures fordeprotecting the amine moiety are from 50 to 250° C., preferably from 75to 200° C., more preferably from 100 to 200° C., and yet more preferablyfrom 125 to 200° C. In general, the treated substrate is heated for aperiod of time from 5 seconds to 60 minutes, preferably from 5 secondsto 30 minutes, and more preferably from 30 seconds to 10 minutes, toremove the solvent and cleave the amine protecting group.

After treating the device substrate with the adhesion promotercomposition, a coating composition comprising an oligomer chosen frompolyarylene oligomers, poly(cyclic-olefin) oligomers, arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof is disposed onthe treated surface, preferably the oligomer is chosen fromarylcyclobutene oligomers, vinyl aromatic oligomers, and mixturesthereof, and more preferably the oligomer is chosen from arylcyclobuteneoligomers. Such composition may be disposed on the substrate using anyof the above-described methods for disposing the adhesion promoter onthe substrate. Typically, the coating composition comprises one or moreoligomers, one or more organic solvents, and optionally one or moreadditional components such as curing agents, coating enhancers, and thelike.

A wide variety of polyarylene oligomers may be used in the presentinvention. As used herein, the term “polyarylene” includes the term“polyarylene ether.” Suitable polyarylene oligomers may be synthesizedfrom precursors such as ethynyl aromatic compounds of the formula:

wherein each Ar is an aromatic group or inertly-substituted aromaticgroup: each R² is independently hydrogen, an alkyl, aryl orinertly-substituted alkyl or aryl group; L is a covalent bond or a groupwhich links one Ar to at least one other Ar; n and m are integers of atleast 2; and q is an integer of at least 1 or from aromatic compoundshaving ethylenically unsaturated terminal groups such as acrylate,methyacrylate, and olefin-containing groups. Suitable polyaryleneoligomers useful in the present invention comprise polymerized units ofthe formula:

wherein Ar′ is the residual of the reaction of product of (C≡C)_(n)—Aror Ar—(C≡C)_(m) moieties and R², L, n and m are as defined above.Polyarylene copolymer oligomers useful in the invention comprisepolymerized units of the formula:

wherein Ar′ and R² are as defined above.

Exemplary polyarylene oligomers include, but are not limited to, thosewherein Ar-L-Ar is: 2,2-diphenylpropane (or —C₆H₄—C(CH₃)₂—C₆H₄—);9,9′-diphenylfluorene; 2,2-diphenyl hexafluoropropane; biphenylene;diphenylsulfide; oxydiphenylene; diphenyl ether;bis(phenylene)diphenylsilane; bis(phenylene)phosphine oxide;bis(phenylene)benzene; bis(phenylene)naphthalene;bis(phenylene)anthracene; thiodiphenylene; 1,1,1-triphenyleneethane;1,3,5-triphenylenebenzene; 1,3,5-(2-phenylene-2-propyl)benzene;1,1,1-triphenylenemethane; naphthylene;1,1,2,2-tetraphenylene-1,2-diphenylethane;bis(1,1-diphenyleneethyl)benzene;2,2′-diphenylene-1,1,1,3,3,3-hexafluoropropane;1,1-diphenylene-1-phenylethane; anthracenylene; andbis(phenylene)napthacene.

Suitable polyarylene oligomers are generally commercially available,such as those sold as SiLK™ Semiconductor Dielectric (available from DowElectronic Materials, Marlborough, Mass.), or may be prepared by avariety of methods known in the art, such as those disclosed in Int.Pat. App. Nos. WO 97/10193, WO 00/31183, WO 98/11149, WO 97/10193, WO91/09081, and U.S. Pat. Nos. 5,115,082; 5,155,175; 5,179,188; 5,874,516;and 6,093,636.

Suitable cyclic-olefin materials are poly(cyclic-olefins), whichpreferably have a weight average molecular weight (M_(w)) of from 2000to 200,000 Daltons, have a softening temperature (melt viscosity at3,000 PaS) of at least 100° C. Preferred poly(cyclic-olefins) arecomprised of recurring monomers of cyclic-olefins and acyclic olefins,or ring-opening polymers based on cyclic-olefins. Suitable cyclicolefins for use in the present invention are chosen fromnorbornene-based olefins, tetracyclododecene-based olefins,dicyclopentadiene-based olefins, and derivatives thereof. Derivativesinclude alkyl (preferably C₁-C₂₀ alkyls), alkylidene (preferably C₁-C₂₀alkylidenes), aralkyl (preferably C₆-C₃₀ aralkyls), cycloalkyl(preferably C₃-C₃₀ cycloalkyls), ether, acetyl, aromatic, ester,hydroxy, alkoxy, cyano, amide, imide, and silyl-substituted derivatives.Particularly preferred cyclic-olefins for use in the present inventioninclude those chosen from

and combinations of the foregoing, where each R³ and R⁴ is independentlychosen from H, and alkyl groups, and each R⁵ is independently chosenfrom H, substituted and unsubstituted aryl groups (preferably C₆-C₁₈aryls), alkyl groups (preferably C₁-C₂₀ alkyls), cycloalkyl groups(preferably C₃-C₃₀ cycloalkyl groups), aralkyl groups (preferably C₆-C₃₀aralkyls, such as benzyl, phenethyl, phenylpropyl, and the like), estergroups, ether groups, acetyl groups, alcohols (preferably C₁-C₁₀alcohols), aldehyde groups, ketones, nitriles, and combinations thereof.Preferred acyclic olefins are chosen from branched and unbranched C₂-C₂₀alkenes.

Suitable cyclic-olefin oligomers are available under the ZEONOR™ (fromZeon Chemicals), ARTON™ (from JSR Corporation), TOPAS™ (available fromTopas Advanced Polymers) and APEL™ (produced by Mitsui Chemicals)brands. Alternatively, suitable cyclic olefin oligomers may be preparedby methods known in the art, such as those described in U.S. Pat. Nos.5,191,026 and 6,008,298.

Arylcyclobutene oligomers are well-known in the art. Suitablearylcyclobutene oligomers include, but are not limited to, those havingthe formula:

wherein B is an n-valent linking group; Ar is a polyvalent aryl groupand the carbon atoms of the cyclobutene ring are bonded to adjacentcarbon atoms on the same aromatic ring of Ar; m is an integer of 1 ormore; n is an integer of 1 or more; and R⁷ is a monovalent group.Preferably, the polyvalent aryl group, Ar, may be composed of 1-3aromatic carbocyclic or heteroaromatic rings. It is preferred that thepolyvalent aryl group comprise a single aromatic ring, and morepreferably a phenyl ring. The polyvalent aryl group is optionallysubstituted with 1 to 3 groups chosen from (C₁-C₆)alkyl,tri(C₁-C₆)alkylsilyl, (C₁-C₆)alkoxy, and halo, preferably with one ormore of (C₁-C₆)alkyl, tri(C₁-C₃)alkylsilyl, (C₁-C₃)alkoxy, and chloro,and more preferably with one or more of (C₁-C₃)alkyl,tri(C₁-C₃)alkylsilyl, and (C₁-C₃)alkoxy. It is preferred that thepolyvalent aryl group is unsubstituted. It is preferred that n=1 or 2,and more preferably n=1. Preferably, m=1-4, more preferably m=2-4, andyet more preferably m=2. It is preferred that R⁷ is chosen from H and(C₁-C₆)alkyl, and more preferably from H and (C₁-C₃)alkyl. Preferably, Bcomprises one or more carbon-carbon double bonds (ethylenicunsaturation). Suitable single valent B groups preferably have theformula —[C(R⁸)═CR⁹]_(x)Z¹, wherein R⁸ and R⁹ are independently chosenfrom hydrogen, (C₁-C₆)alkyl, and aryl; Z¹ is chosen from hydrogen,(C₁-C₆)alkyl, aryl, siloxanyl, —CO₂R¹⁰; each R¹⁰ is independently chosenfrom H, (C₁-C₆)alkyl, aryl, aralkyl, and alkaryl; and x=1 or 2.Preferably, R⁸ and R⁹ are independently chosen from H, (C₁-C₃)alkyl, andaryl, and more preferably H and (C₁-C₃)alkyl. It is preferred that R¹⁰is (C₁-C₃)alkyl, aryl, and aralkyl. Z¹ is preferably siloxyl. Preferredsiloxyl groups have the formula —[Si(R¹¹)₂—O]p-Si(R¹¹)₂—, wherein eachR¹¹ is independently chosen from H, (C₁-C₆)alkyl, aryl, aralkyl, andalkaryl; and p is an integer from 1 or more. It is preferred that R¹¹ ischosen from (C₁-C₃)alkyl, aryl, and aralkyl. Suitable aralkyl groupsinclude benzyl, phenethyl and phenylpropyl.

Preferably, the arylcyclobutene oligomers comprise one or more oligomersof the formula:

wherein each R¹² is independently chosen from H and (C₁-C₆)alkyl, andpreferably from H and (C₁-C₃)alkyl; each R¹³ is independently chosenfrom (C₁-C₆)alkyl, tri(C₁-C₆)alkylsilyl, (C₁-C₆)alkoxy, and halo; eachR¹⁴ is independently a divalent, ethylenically unsaturated organicgroup; each R¹⁵ is independently chosen from H, (C₁-C₆)alkyl, aralkyland phenyl; p is an integer from 1 or more; and q is an integer from0-3. Each R¹² is preferably independently chosen from H and(C₁-C₃)alkyl, and more preferably each R¹² is H. It is preferred thateach R¹³ is independently chosen from (C₁-C₆)alkyl,tri(C₁-C₃)alkylsilyl, (C₁-C₃)alkoxy, and chloro, and more preferablyfrom (C₁-C₃)alkyl, tri(C₁-C₃)alkylsilyl, and (C₁-C₃)alkoxy. Preferably,each R¹⁴ is independently chosen from a (C₂-C₆)alkenyl, and morepreferably each R¹⁴ is —CH═CH—. Each R¹⁵ is preferably chosen from(C₁-C₃)alkyl, and more preferably each R¹⁵ is methyl. Preferably, p=1-5,more preferably p=1-3, and yet more preferably p=1. It is preferred thatq=0. A particularly preferred arylcyclobutene oligomer,1,3-bis(2-bicyclo[4.2.0]octa-1,3,5-trien-3-yl ethenyl)-1,1,3,3tetramethyldisiloxane (“DVS-bisBCB”), has the formula

Arylcyclobutene oligomers may be prepared by any suitable means, such asthose described in U.S. Pat. Nos. 4,812,588; 5,136,069; 5,138,081; andInt. Pat. App. No. WO 94/25903. Suitable arylcyclobutene oligomers arealso commercially available under the CYCLOTENE™ brand, available fromDow Electronic Materials. The arylcyclobutene oligomers may be used asis, or may be further purified by any suitable means.

Vinyl aromatic oligomers are well-known in the art. Such vinyl aromaticoligomers include oligomers of only vinyl aromatic monomers andoligomers of vinyl aromatic monomers with one or more reactiveethylenically unsaturated co-monomers. Suitable vinyl aromatic monomersare unsubstituted vinyl aromatic monomers and substituted vinyl aromaticmonomers where one or more hydrogens are replaced with a substituentgroup selected from the group of (C₁-C₆)alkyl, (C₁-C₆)alkoxy, halo, andamino. Exemplary vinyl aromatic monomers include, without limitation,styrene, vinyltoluene, vinylxylene, vinylanisole, vinyldimethoxybenzene,vinylaniline, halostyrene such as fluorostyrene, α-methylstyrene,β-methoxystyrene, ethylvinylbenzene, vinylpyridines, vinylimidazoles,vinylpyrroles, and mixtures thereof. Preferred reactive co-monomers arethose comprising a reactive moiety, that is, a moiety capable of furtherpolymerization (or crosslinking) following formation of the vinylaromatic oligomer, such as an allyl moiety or a vinyl group, in additionto an olefinic (or ethylenically unsaturated) moiety used to for thevinyl aromatic oligomer. More preferably, the reactive co-monomerscomprise an allyl moiety in addition to the ethylenic unsaturation usedto form the vinyl aromatic oligomer. Exemplary reactive co-monomersinclude, but are not limited to, vinylcyclohexene, vinyl ethers,asymmetrical dienes or trienes such as terpene monomers, diallylmaleate, allyl acrylate, allyl methacrylate, allyl cinnamate, diallylfumerate, allyl tiglate, divinylbenzene, and mixtures thereof. It willbe appreciated by those skilled in the art that one or more secondaryco-monomers may also be used to form the vinyl aromatic oligomers. Suchsecondary co-monomers are ethylenically unsaturated, but do not containa reactive moiety. Exemplary secondary co-monomers include, but are notlimited to, (meth)acrylic acid, (meth)acrylamides,(C₁-C₁₀)alkyl(meth)acrylates, aromatic(meth)acrylates, substitutedethylene monomers, and poly(alkylene oxide)monomers.

The molar ratio of vinyl aromatic monomers to co-monomers in such vinylaromatic oligomers is preferably from 99:1 to 1:99. Typically, vinylaromatic oligomers are prepared by free-radical polymerization of avinyl aromatic monomer and a co-monomer, but may be prepared by anymethod known in the art.

The coating compositions are prepared by combining one or more oligomersas described above with one or more organic solvents, and one or moreoptional components. It is preferred that the oligomer is anarylcyclobutene oligomer. Suitable organic solvents include thosedescribed above for use in the adhesion promoter compositions. Exemplaryoptional components in the coating compositions include one or morecuring agents, one or more anti-oxidants, and the like. Curing agentsmay aid in the curing of the oligomers, and may be activated by heat orlight. Suitable curing agents include thermally generated initiators andphotoinitiators. The selection of such curing agents is well within theability of those skilled in the art. The amount of the oligomers,solvents and optional components in the coating composition may varyacross a wide range and is within the ability of one skilled in the art.It will be appreciated by those skilled in the art that the solidscontent in the coating compositions may be adjusted, along with the spinspeed, to achieve a desired thickness of the coating composition on theadhesion promoter treated surface.

The coating compositions may be disposed (or coated) on the adhesionpromoted device substrate surface by any suitable method, such as thosedescribed above for disposing the adhesion promoter on the devicesubstrate. Such methods of depositing coating compositions arewell-known in the art. After being disposed on an adhesion promotedsurface, the coating compositions are typically cured using theappropriate method for the oligomer selected. Such curing methods arewell-known in the art. For example, arylcyclobutene oligomers may becured by heating, or in the case of photodefinable arylcyclobuteneoligomers by exposure to actinic radiation (light) of an appropriatewavelength.

Also provided by the present invention is a self-priming coatingcomposition comprising a hydrolyzed amino-alkoxysilane having aprotected amino moiety, water, organic solvent, and a coating oligomerchosen from polyarylene oligomers, poly(cyclic-olefin) oligomers,arylcyclobutene oligomers, vinyl aromatic oligomers, and mixturesthereof. Preferably, the coating oligomer is chosen from arylcyclobuteneoligomers, vinyl aromatic oligomers, and mixtures thereof, and morepreferably the coating oligomer is an arylcyclobutene oligomer.Optionally, these self-priming compositions may comprise one or moreadditional components such as anti-oxidants, photo-cross-linking agents,and coating enhancers. Such optional components are well-known to thoseskilled in the art. Any of the hydrolyzed amino-alkoxysilanes describedabove may be used in this composition. Any of the oligomers describedabove for the coating composition may be used in this self-primingcomposition, and preferably the oligomer is an arylcyclobutene oligomer.Suitable organic solvents are those described above for use in theadhesion promoter compositions. As used herein, the term “self-primingcoating composition” refers to a composition comprising an adhesionpromoting hydrolyzed amino-alkoxysilane water, organic solvent, and acoating oligomer. An advantage of these self-priming coatingcompositions is that a separate step of applying an adhesion promotercan be avoided. Alternatively, these self-priming coating compositionsmay be used to form a first coating layer, upon which subsequent coatinglayers are deposited. In certain applications, the use of a self-primingcoating composition is preferred over the use of a separate adhesionpromoter composition. Such self-priming compositions may suitably beused to form dielectric coatings, photodefinable coatings, temporaryadhesives, permanent adhesives, and the like.

The amounts of the hydrolyzed amino-alkoxysilane, water, organic solventand coating oligomer employed in the self-priming coating compositiondepends upon a number of factors including the specific end-useapplication and the properties desired. If the self-priming coatingcomposition is intended to have one or more coating oligomer layerssubsequently applied to it, the self-priming coating composition willtypically contain lesser amounts of the coating oligomer than when nosubsequent coating oligomer layer is used. In general, regardless of itsintended end-use, the self-priming coating composition comprises from0.01 to 10 wt % of hydrolyzed amino-alkoxysilane, from 0.01 to 3 wt %water, from 10 to 99.98 wt % organic solvent, and from 0.01 to 90 wt %coating oligomer, where the weight percents are based on the totalweight of the composition. Preferably, the self-priming coatingcompositions comprise form 0.01 to 5 wt % of hydrolyzedamino-alkoxysilane, more preferably from 0.01 to 3 wt %, and even morepreferably from 0.01 to 2 wt %. When subsequent coating oligomercompositions will be disposed on the self-priming composition, it ispreferred that the coating oligomers in the self-priming coatingcompositions are present in an amount of ≧0.01, more preferably ≧1, evenmore preferably from 2 to 20 wt %, and yet more preferably from 5 to 20wt %. When subsequent coating oligomer compositions will not be disposedon the self-priming coating, it is preferred that the coating oligomerbe present in the composition in an amount of ≧5, more preferably ≧10,and yet more preferably from 20 to 90 wt %. Preferred amounts of watervary from 0.05 to 2 wt %. Preferred amounts of organic solvent vary from10 to 98 wt %, more preferably from 20 to 90 wt %, and still morepreferably from 20 to 75 wt %. In one embodiment, the compositioncomprises from 0.01 to 10 wt % of hydrolyzed amino-alkoxysilane having aprotected amino moiety, from 0.05 to 2 wt % water, from 40 to 99.5 wt %of organic solvent; and from 1 to 80 wt % of coating oligomer, based onthe total weight of the composition. In another embodiment, thecomposition comprises from 0.01 to 10 wt % of hydrolyzedamino-alkoxysilane having a protected amino moiety, from 0.05 to 2 wt %water, from 10 to 99.9 weight percent of organic solvent, and from 0.01to 90 percent by weight of coating oligomer, based on the total weightof the composition.

The self-priming coating compositions may be disposed on a devicesubstrate to form a coated film using any of the methods described abovefor the adhesion promoting compositions. Spin-coating is a preferredmethod. Following deposition on a device substrate, the coated film istypically cured, such as by heating, exposure to actinic radiation(light), or a combination thereof. Photodefineable arylcyclobutenes aretypically photocrosslinked prior to further cure. The specific curingconditions used depend on the particular oligomer selected, theparticular application such as whether the coated film is a dielectricor an adhesive, as well as on other parameters known to those skilled inthe art.

EXAMPLE 1

An adhesion promoting composition of the invention was prepared bycombining bis(3-(trimethoxysilyl)propyl)amine (0.41 wt %, 1.2 mmol),(3-(2-aminoethylamino)propyl)trimethoxysilane (0.21 wt %, 1.9 mmol basedon the amino moiety), and PGME (99.38 wt % and having residual waterpresent). The composition was aged overnight at room temperature. Next,di-t-butyl dicarbonate (0.6 wt %, 2.7 mmol) was added to the compositionand the composition was allowed to react overnight to provide a mixtureof a majority of hydrolyzed silanes with t-BOC protected amino moietiesand a minority of hydrolyzed silanes with unprotected amino moieties.The composition (Sample 1) was next filtered through 20 nm polypropylenefilter. Water present in the solvent and residual amine functionalitywere present in this sample enabling hydrolysis of the silane.

EXAMPLE 2

The compatibility of Sample 1 with a base-reactive photodielectric wasevaluated. Sample 1 and a commercially available developablebenzocyclobutene photodielectric having acidic functionality werecombined 1:1 weight ratio in a glass, screw-top vial, forming a clearsolution.

COMPARATIVE EXAMPLE 1

A comparative adhesion promoting composition (Comparative 1) wasprepared by combining bis(3-(trimethoxysilyl)propyl)amine (0.41 wt %),(3-(2-aminoethylamino)propyl)trimethoxysilane (0.21 wt %), and PGME(99.38 wt %). The composition was aged overnight at room temperature.Comparative 1 was combined with the commercially available developablebenzocyclobutene photodielectric having acidic functionality fromExample 2 in a 1:1 weight ratio in a glass, screw-top vial. Aprecipitate formed upon the mixing of Comparative 1 with thephotodielectric material.

EXAMPLE 3

The adhesion promoters of Sample 1 and Comparative 1 were evaluatedusing a lithographic printing test. Each of Sample 1 and Comparative 1was coated on a 200 mm test wafer using a Site Trac TT5-XP coater at aspin speed of 2000 rpm for 40 seconds followed by a 90° C. or 180° C.bake for 90 seconds to ensure solvent removal. No coating defects wereobserved for any adhesion promoter sample. The post bake coatingthicknesses of the adhesion promoters are reported in Table 1. As can beseen from the data, the coating thickness of Sample 1 baked at 180° C.is much lower than when baked at 90° C. This difference in filmthickness is indicative of deprotection of the amine moieties of thehydrolyzed amino-alkoxysilanes.

A benzocyclobutene dielectric resin was coated on each adhesion promotedwafer using a Site Trace TT6-XP at a spin speed around 1500 rpm totarget a film thickness of approximately 6.5 μm. The spin coateddielectric was then soft baked at 90° C. for 90 seconds to ensuresolvent removal. Next, the dielectric-coated wafers were exposed on anASML 200 i-line stepper using a bright field reticle to print to printrows of variously sized posts (from 1 to 25 μm) on the wafer. Afterexposure, a 15 minute post exposure hold was utilized to allow moisturediffusion back into the film. After exposure, the exposed areas of thedielectric resin were developed on a Site Trac TTP-X5 using a CD-26developer solution employing a 60 second single puddle followed by a 90second de-ionized water rinse. The post printing resolution is reportedin Table 1. The post printing resolution is the minimum feature sizeremaining after development. As can be seen from the data in Table 1,the best resolution was achieved using Sample 1 that had been baked at180° C. to cleave the amino protecting moiety.

TABLE 1 Adhesion Promoter Bake Coating Printed Post Sample Temperaturethickness Resolution Sample 1 90° C. 328 Å 5 μm Sample 1 180° C.  102 Å2 μm Comparative 1 90° C. 161 Å 4 μm

EXAMPLE 4

An adhesion promoting composition of the invention was prepared bydissolving bis(3-(triethoxysilyl)propyl)amine (0.5 wt %) in a 95/5 w/wsolvent mixture of propylene glycol methyl ether (PGME)/dipropyleneglycol methyl ether (DPGME), then adding 1.2 molar amine equivalents ofdi-t-butyl dicarbonate to the composition, and allowing the mixture toreact overnight to provide t-BOC protected amino moiety. Next, 2000 ppmof nitric acid and 1.18 wt % water were added and the composition wasallowed to react to provide a hydrolyzed amino-alkoxysilane having aprotected amino moiety (Sample 2), followed by filtration through a 0.1μm polypropylene filter.

Sample 2 was combined with a commercially available base-reactivedielectric (CYCLOTENE™ 6505 resin, available from Dow ElectronicMaterials, Marlborough, Mass.) in a 9.5:5 weight ratio in a glassscrew-capped vial. The mixture of Sample 2 and the dielectric materialshowed no precipitate formation.

Sample 2 was coated on a 200 mm silicon wafer according to the processof Example 3. Visual inspection showed no coating defects. The thicknessof the adhesion promoting layer on the wafer was 133 Å as coated, andfollowing baking at 150° C. for 60 seconds, the thickness of the of theadhesion promoting layer was 125 Å.

EXAMPLE 5

The procedure of Example 4 was repeated except that 1.58 equivalents ofdi-t-butyl dicarbonate were used, the PGME/DPGME ratio was 90/10, and 1wt % of water was used. Visual inspection of the coated wafer showed nocoating defects. The thickness of the adhesion promoting layer on thewafer was 124 Å as coated, and following baking was 114 Å.

EXAMPLE 6

An adhesion promoting composition of the invention was prepared bydissolving aminopropyl triethoxysilane in PGME, then adding 1.2 molarequivalents of di-t-butyl dicarbonate, and allowing the mixture to reactovernight to provide t-BOC protected amino moiety. The total solidscontent in the composition was approximately 0.1%. Next 0.12 wt % ofwater was added and the composition allowed to react for 8 days toprovide a hydrolyzed amino-alkoxysilane having a protected amino moiety(Sample 3). Four 200 mm wafers were coated with Sample 3 according tothe procedure of Example 3. Visual inspection of all wafers showed nocoating defects. One coated wafer was then baked at each of 175, 200,225 and 250° C. for 60 seconds.

EXAMPLE 7

An adhesion promoting composition of the invention was prepared bydissolving bis-(triethoxysilylpropyl)amine in 90/10 PGME/DPGME, thenadding 1.58 molar equivalents of di-t-butyl dicarbonate, and allowingthe mixture to react overnight to provide t-BOC protected amino moiety.Next 1 wt % of water and 2000 ppm of nitric acid were added and thecomposition allowed to react to provide a hydrolyzed amino-alkoxysilanehaving a protected amino moiety (Sample 4).

EXAMPLE 8

The procedure of Example 7 was repeated except that the solvent was 95/5w/w PGME/DPGME and 1.2 equivalents of di-t-butyl dicarbonate were usedto produce Sample 5.

EXAMPLE 9

The procedure of Example 8 was repeated except that thebis-(triethoxysilylpropyl)amine was replaced withbis-(trimethoxysilylpropyl)amine to provide Sample 6.

EXAMPLE 10

Each of Samples 4-6 were used to coat 200 mm wafers according to theprocedure of Example 3. Visual inspection of the coated wafers showed nocoating defects. The thickness of each adhesion promoter coating wasapproximately 130 Å as coated. The adhesion promoter coatings were bakedat 150° C. for 60 seconds, and the film thicknesses were again measuredand found to be on average 123 Å. A benzocyclobutene dielectric resinwas coated on each of the adhesion promoted wafers and posts werelithographically printed according to the procedure of Example 3. Thepost printing resolution for each of Samples 4-6 was 1 to 2 μm.

EXAMPLE 11

An adhesion promoting composition of the invention is prepared bydissolving N¹,N¹-bis(3-(trimethoxysilyl)propyl)ethane-1,2-diamine (0.75wt %) in PGME, then adding 1.2 molar equivalents of di-t-butyldicarbonate. The mixture is allowed to react overnight to provide t-BOCprotected amino moiety. Next, 2000 ppm of nitric acid and 2 wt % waterare added and the composition is allowed to react to provide ahydrolyzed amino-alkoxysilane having a protected amino moiety (Sample7).

EXAMPLE 12

An adhesion promoting composition of the invention is prepared bydissolving3-(trimethoxysilyl)-N-(2-(trimethyoxysilyl)ethyl)-N-(3-(trimethoxysilyl)propyl)-propan-1-amine(0.5 wt %) in 95/5 w/w PGME/DPGME, then adding 1.25 molar equivalents ofdi-t-butyl dicarbonate. The mixture is allowed to react overnight toprovide t-BOC protected amino moiety. Next, 2000 ppm of nitric acid and2 wt % water are added and the composition is allowed to react toprovide a hydrolyzed amino-alkoxysilane having a protected amino moiety(Sample 8).

EXAMPLE 13

A self-priming coating composition is prepared by combining 83.63 g of40 wt % solution of aqueous developable, benzocyclobutene resin(Cyclotene™ 6505 resin) in a mixed solvent system of PROGLYDE™ DMM,PGMEA, anisole and 0.25 wt % of Sample 2. The composition is thenthoroughly mixed. The composition is then spin-coated on a 200 mm wafer.

EXAMPLE 14

The procedure of Example 13 is repeated except that the compositionfurther contains 250 ppm of tolyltriazole as a metal passivating agent.

EXAMPLE 15

The procedure of Example 13 is repeated except that the compositionfurther contains a thermal acid generator in a molar ratio of thermalacid generator to Sample 2 of 0.8:1.

COMPARATIVE EXAMPLE 2

Bis(trimethoxysilylpropyl)amine (0.4 g) was added to 99.6 g of a 95/5 wt% blend of PGME/DPGME followed by mixing for 10 minutes. Next, 0.31 g ofdi-(t-butyl dicarbonate) was added and mixed for 120 minutes. The amountof the di-(t-butyl dicarbonate) was 1.2 molar equivalents to that of theaminosilane to ensure complete protection of the amine. The sample wasaged for 10 days prior to testing. Since no water was added to thereaction mixture, the protected amino-alkoxysilane reaction product wasnot hydrolyzed. After aging, the sample was coated on a 200 mm siliconwafer at 2000 rpm for 30 seconds. Film thickness was measured and thefilm was then baked at 150° C. for 60 seconds. Film thickness was thenre-measured after baking to determine if there was a change inthickness. The quality of the film as coated was good. However, 100%film loss was observed after the baking step indicating that theprotected bis(trimethoxysilylpropyl)amine evaporated during the bakingstep.

COMPARATIVE EXAMPLE 3

The procedure of Comparative Example 2 was repeated except that 1.18 gof water was added prior to aging the sample to determine if water alonewas sufficient for hydrolysis. The amount of water was approximately 9molar excess per methoxy unit. The sample was aged for 10 days prior totesting. After aging, the sample was coated on a 200 mm silicon wafer at2000 rpm for 30 seconds. Film thickness was measured and the film wasthen baked at 150° C. for 60 seconds. Film thickness was thenre-measured after baking to determine if there was a change inthickness. The quality of the film as coated was good. However, 100%film loss was observed after the baking step indicating that theprotected bis(trimethoxysilylpropyl)amine evaporated during the bakingstep. Excess water alone is insufficient to hydrolyze the protectedamino-alkoxysilane.

COMPARATIVE EXAMPLE 4

The procedure of Comparative Example 3 was repeated except that thebis(trimethoxysilylpropyl)amine was replaced with 0.5 g ofbis(triethoxysilylpropyl)amine and 99.5 g of PGME/DPGME was used. Thesample was coated on a 200 mm silicon wafer at 2000 rpm for 30 seconds.The quality of the coating was poor, forming droplets rather than auniform coating, making film thickness measurements very difficult. Thefilm thickness was baked at 150° C. for 60 seconds. After baking, 100%loss of the droplets was observed leaving only a bare silicon wafer.This implies the protected amino-alkoxysilane did not crosslink duringthe bake step. Further aging of the sample for 30 days prior to filmcoating did not change the results.

EXAMPLE 16

Bis(triethoxysilylpropyl)amine (0.5 g) was added to 99.5 g of a 95/5 wt% blend of PGME/DPGME and was mixed for 10 minutes. Next, 0.31 g ofdi-(t-butyl dicarbonate) was added and mixed for 120 minutes. The amountof the di-(t-butyl dicarbonate) was used in a 1.2 molar excess comparedto the aminosilane to ensure complete protection of the amine Next, 1.0g of water and 1.0 g of a 20 wt % nitric acid solution in PGME was addedfollowed by mixing for 60 minutes before aging 1 day prior to testing.The resulting nitric acid concentration was 2000 ppm. After one day ofaging, the sample was coated on a 200 mm silicon wafer at 2000 rpm for30 seconds. The quality of the coating was good. The loss in filmthickness after baking was found to be approximately 5.3% indicating across-linked film was obtained.

EXAMPLE 17

The procedure of Example 16 was repeated except that thebis(triethoxysilylpropyl)amine was replaced with 0.4 g ofbis(trimethoxysilylpropyl)amine and 99.6 g of the PGME/DPGME solventmixture was used. The resulting nitric acid concentration was 2000 ppm.After one day of aging, the sample was coated on a 200 mm silicon waferat 2000 rpm for 30 seconds. The quality of the coating was good. Theloss in film thickness after baking was found to be 4.6% indicating across-linked film was obtained.

COMPARATIVE EXAMPLE 5

3-Aminopropyl triethoxysilane (1.1 g) was combined with 1.2 g water andmixed for 30 minutes to ensure full hydrolysis of the silane. Aftermixing, the hydrolyzed concentrate was diluted with 997.7 g PGME andmixed for another 30 minutes. The level of water corresponds toapproximately 4.5 molar excess per ethoxy unit (0.12 wt % based on theweight of the composition).

EXAMPLE 18

3-Aminopropyl triethoxysilane (1.1 g) was combined with 1.2 g water andmixed for 30 minutes to ensure full hydrolysis of the silane. Next,di-(t-butyl dicarbonate) (1.3 g, 1.2 molar equivalents of the aminemoiety) was added followed by mixing for 120 minutes. After mixing, thehydrolyzed concentrate was diluted with 997.7 g PGME and mixed foranother 30 minutes. The level of water corresponds to approximately 4.5molar excess per ethoxy unit (0.12 wt % based on the weight of thecomposition).

EXAMPLE 19

Samples of each of Comparative Example 3, Comparative Example 5, andExample 18 were aged for eight days. Films of each of the samples werespin coated on 200 mm silicon wafers at 2000 rpm for 30 seconds. Thequality of each of the coated films was good The films were then bakedat 150° C. for 60 seconds. Film thickness measurements indicated thefollowing approximate film thickness losses: Comparative Example 3 (4%),Comparative Example 5 (5%), and Example 18 (2%).

A benzocyclobutene dielectric resin (CYCLOTENE™ 6505 Photodielectricresin) was coated on each adhesion promoted wafer using a Site TraceTT6-XP at a spin speed around 1500 rpm to target a film thickness ofapproximately 6.5 μm. The spin coated dielectric was then soft baked at90° C. for 90 seconds to ensure solvent removal. Next, thedielectric-coated wafers were exposed on an ASML 200 i-line stepperusing a bright field reticle to print to print rows of variously sizedposts (from 1 to 25 μm) on the wafer. After exposure, a 15 minute postexposure hold was utilized to allow moisture diffusion back into thefilm. After exposure, the exposed areas of the dielectric resin weredeveloped on a Site Trac TTP-X5 using a CD-26 developer solution (0.26 Ntetramethylammonium hydroxide) employing a 60 second single puddlefollowed by a 90 second de-ionized water rinse. The wafers were thenevaluated for post printing resolution which is the minimum feature sizeremaining after development. The imaged dielectric resin on the wafertreated with the sample from Comparative Example 3 completelydelaminated after contact with the developer solution. The imageddielectric resin on the wafer treated with the sample from ComparativeExample 5 showed better performance than Comparative Example 3, butstill showed delamination of smaller posts. The imaged dielectric resinon the wafer treated with the sample from Example 18 showed excellentpost adhesion with 1 and 2 μm posts remaining after contact with thedeveloper solution.

What is claimed is:
 1. A composition comprising: one or more hydrolyzedamino-alkoxysilanes having a protected amino moiety; water; and organicsolvent.
 2. The composition of claim 1 further comprising one or moreoligomers chosen from polyarylene oligomers, poly(cyclic-olefin)oligomers, arylcyclobutene oligomers, vinyl aromatic oligomers, andmixtures thereof.
 3. The composition of claim 1 wherein the compositionfurther comprises a metal passivation agent.
 4. The composition of claim1 wherein the protected amino moiety is cleavable with heat, acid or acombination thereof.
 5. The composition of claim 1 wherein thehydrolyzed amino-alkoxysilane is a hydrolyzed amino-poly(alkoxysilane).6. The composition of claim 5 wherein the hydrolyzedamino-poly(alkoxysilane) has the formula:

wherein each R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; each R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; each Z isindependently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and —OR¹; andY=an amine protecting group; wherein each R is optionally substitutedwith one or more of —(C₁-C₆)alkylidene-SiZ₂(OR¹) and—(C₁-C₆)alkylene-SiZ₂(OR¹), and wherein at least one R¹ is H.
 7. Thecomposition of claim 1 wherein the hydrolyzed amino-alkoxysilane has theformula:

wherein R is independently chosen from (C₁-C₆)alkylidene,(C₁-C₆)alkylene, (C₆-C₁₀)arylene, and (C₂-C₆)alkenylene; R¹ isindependently chosen from H, (C₁-C₆)alkyl and (C₁-C₆)acyl; R² is chosenfrom H, —R—SiZ₂(OR¹), (C₁-C₆)alkyl, (C₆-C₁₀)aryl and (C₇-C₁₅)alkaryl;each Z is independently chosen from (C₁-C₆)alkyl, (C₂-C₆)alkenyl and—OR¹; and Y=an amine protecting group; wherein each R is optionallysubstituted with one or more of —(C₁-C₆)alkylidene-SiZ₂(OR¹) and—(C₁-C₆)alkylene-SiZ₂(OR¹), and wherein at least one R¹ is H.
 8. Thecomposition of claim 1 wherein the protected amino moiety is chosen from9-fluorenylmethyl carbamate, t-butyl carbamate, benzyl carbamate,acetamide, trifluoroacetamide, benzylamine, tritylamine,benzylideneamine, and tosylamide.
 9. The composition of claim 1 furthercomprising a hydrolyzed amino-alkoxysilane having an unprotected aminomoiety.
 10. A process for manufacturing an electronic device,comprising: providing an electronic device substrate having a surface tobe coated; treating the surface to be coated with the composition ofclaim 1; disposing a coating composition comprising an oligomer chosenfrom polyarylene oligomers, poly(cyclic-olefin) oligomers,arylcyclobutene oligomers, vinyl aromatic oligomers, and mixturesthereof on the treated surface; and curing the coating composition. 11.A process for manufacturing an electronic device, comprising: providingan electronic device substrate having a surface to be coated; treatingthe surface to be coated with the composition of claim 2; and curing theoligomer.